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Mineralogy and rare earth elements in

sediment cores from the Mandovi estuary,
western India: Inferences on sources of the
sediments

Poster · March 2015

DOI: 10.13140/RG.2.2.28708.27525

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 Mineralogy and rare earth elements in sediment cores from the Mandovi
estuary, western India: Inferences on sources of the sediments
A. Prajith, V. Purnachandra Rao, and Pratima M. Kessarkar OSICON – 15
CSIR- National Institute of Oceanography, Dona Paula, Goa-403 004 March 22-24, 2015

The rare earth elements (REE), La to Lu, are members of Group IIIA in the periodic table particularly 3+ oxidation state and all have similar chemical and physical properties. REEs have been
widely used as traces of geochemical processes in a variety of sedimentary environments because of their similar chemical behavior. However, cerium (Ce) and europium (Eu) are redox
sensitive element, oxidation of Ce3+ to Ce4+ and reduction of Eu3+ to Eu2+ can be used as an indicator of reducing conditions in the sedimentary environment . We investigate here the
mineralogy and REEs of bulk sediments in the gravity cores collected along transect of the Mandovi estuary, western India to determine sources and controls on REE distribution. The
Mandovi estuary is a tropical, monsoonal estuary. The estuarine sedimentation in Mandovi estuary is mainly influenced by detrital sediments, ore material and organic sediments. Goa is
dominantly covered by the rocks of Goa Group, belonging to the Dharwar Super Group of Archean-Proterozoic age and the late Cretaceous Deccan Trap found only at the northeastern part of
Goa (Fig. 1). Since 1940, mining for Fe-Mn ores is an important activity in the drainage basin of the Mandovi River.

REE showed strong positive correlation with clay fractions

(Fig. 4A) and were higher in clayey silts than in sand/sandy
silts (Fig. 3A-D). The correlation of REE with OC was
increased towards bay sediments (Fig. 4B).

Fig. 1. Map showing the location of sediment cores in the Mandovi

estuary, western India. Upper estuary, middle estuary and lower estuary
and bay are marked in the figure. Geology of the Mandovi River basin,
locations of iron ore loading docks, iron ore plant and shipping plant
along the shore of the estuary are also shown.
Fig. 4. Correlations of REE with total clay (A) and organic carbon
Materials and Methods (OC) (B), OC with Ce/Ce* (C), and Eu/Eu* (D).

The total organic carbon (TOC) ages of sediments in cores

at different intervals were measured by Accelerator Mass
Spectrometer (AMS) at NOSAMS facility, Woods Hole
Oceanographic Institution, USA.
The grain size analysis of sediments was carried out by
using laser Malvern Laser Particle size analyzer (Master
sizer 2000).
The total carbon content of the sediments was determined
by using NC soil analyzer (FLASH 2000 Organic Elemental
Analyzer). The total inorganic carbon content was
calculated from CaCO3 content, which was measured using
a coulometer (UIC, Inc-CM5130 acidification module).
Organic carbon (OC) content was then calculated by
subtracting total inorganic carbon from the total carbon in
the sediments.
The bulk mineralogy analysis was carried out by using
Rigaku X-ray diffractometer.
The Perkin Elmer Optical Emission Spectrometer (Optima
7300 DV) and Inductively-coupled plasma Mass
Spectrometer (ICP-MS-Thermo X series 2) were used for
determination of REEs and major metals concentrations,
Fig. 3. Down core distribution of various parameters. Vertical dashed
respectively. lines on the down core distribution of Y/Ho and Sm/Nd ratios represent
their PAAS values.
Results
The gradual decrease of Fe, Mn and Ce/Ce* with
Quartz was the predominant mineral in sediments of all increasing of OC and (La/Yb)n towards core top of the Fig. 5. PAAS-normalized rare earths and yttrium (REY) patterns of
cores. The upper and middle estuary sediments showed sediments.
upper estuary (Fig. 3A) and inverse correlation between
higher proportion of iron ore minerals than in lower estuary /
Aguada Bay. The sandy sediments from the middle estuary OC and Ce anomaly (Fig. 4C) indicated reduction of Fe, Mn Conclusions
and bay showed high proportions of feldspars (Fig. 2). and Ce in early diagenetic conditions and preferential
adsorption of LREE onto OC. Moreover, there is no change • REE of sediments are primarily controlled by its texture
in REE profile indicates its immobility during diagenesis. and source sediment.

Fig. 2. X-ray diffractogram. Q-quartz, H-hematite, M-magnetite, G-
goethite, P-F Plagioclase feldspar, K-F – potash feldspar.
REE of sediments varied from 37 to 160 g/g in different
cores and were lower than in Post-Archean Australian
Shale (PAAS; 185 g/g) (McLennan, 1989). The light to
heavy REE ratios (LREE/HREE) of sediments (ranges from
15.8 to 18.7) were also lower than in PAAS (24.7).
High positive Eu/Eu* values were associated with high
sand content in the bay and middle estuary that contain
both K- and plagioclase feldspars (Fig. 3B & D).
High Y/Ho ratios in clayey silts are due to redistribution of Y
and Ho by adsorption onto organic-rich, clays. Variations in
Sm/Nd ratios are similar to that of Eu/Eu* in cores from the
lower estuary/bay and are controlled by mineral
constituents of the sediments.
The PAAS-normalized rare earths and yttrium patterns of
sediments showed middle REE (MREE)- and HREE-
enrichment with positive Eu anomaly (Eu/Eu*) and variable
Ce anomaly (Ce/Ce*) (Fig. 5A-D). Positive Ce and Eu
anomalies are inherited from ore material (Fig. 5A). The
MREE- and HREE enriched patterns with positive Eu
anomaly in sediments of the lower estuary/bay (Figs. 5C-D)
largely resemble that of Tonalite-Trondhjemite Gneisses
(Fig. 5C) and mafic-ultramafic rocks from Goa region
(Dhoundial et al., 1987).
• The mineralogy and REEs in cores sediments from the
Mandovi estuary indicate ore material dominated in the
upper/middle estuary and detrital dominated sediments in
the lower estuary/bay.
• Low LREE/HREE ratios suggest loss of fine-grained
weathering material from the estuary because of high
energy conditions.
Acknowledgements
We thank the Director, National Institute of Oceanography for the
facilities and encouragement. Prajith thanks the University Grants
Commission (UGC) for awarding research fellowship.
References
Dhoundial, D.P., Paul, D.K., Sarkar, A., Trivedi, J.R., Gopalan, K., Potts, P.J., 1987.
Geochronology and geochemistry of the Precambrian granitic rocks of Goa, SW
India. Precambrian Research 36, 287-302.
McLennan, S.M., 1989. Rare earth elements in sedimentary rocks: influence of
provenance and sedimentary processes. In: Lipin B.R. and G.A. Mckay (editors),
Geochemistry and mineralogy of rare earth elements. Reviews in Mineralogy 21,
169-200.

CSIR-National Institute of Oceanography, Goa

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